Alkoxylaton process using calcium based catalysts

ABSTRACT

A process for preparing an alkoxylation catalyst in which the catalyst pre-mix is formed by admixing an alkoxylated alcohol with a calcium containing compound which is dispersible in the alkoxylated alcohol, an inorganic acid and an aluminum trialkoxide, the pre-mix being heated to a temperature and for a time sufficient to effect at least partial exchange reaction betweeen the alkoxide groups of the aluminum alkoxide and the hydroxyl groups of the alkoxylated alcohol. There is also disclosed and claimed an alkoxylation process utilizing the catalysts formed as described above.

This is a division of application Ser. No. 043,660, filed Apr. 28, 1987,now U.S. Pat. No. 4,775,653.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for the preparation ofalkylene oxide adducts of active hydrogen compounds such as alcohols andto a process for preparing catalysts useful in such alkoxylationreactions.

2. Description of the Prior Art

Alkylene oxide adducts of hydrogen compounds find utility in a varietyof products such as, for example, surfactants, solvents, chemicalintermediates, etc. Typically, these alkylene oxide adducts are preparedby an addition or alkoxylation reaction in which an alkylene oxide, suchas ethylene oxide, is reacted under suitable conditions with an organiccompound, such as an alcohol, having one or more active hydrogen atoms.In particular, ethylene oxide adducts of aliphatic alcohols orsubstituted phenols having from about 8 to 20 carbon atoms have foundwidespread utility as non-ionic detergent components of cleaningformulations for use in industry and in the home.

The alkoxylation reaction produces a product mixture of variousalkoxylate molecules having a variety of alkylene oxide adducts(oxyethylene adducts). Because the number of oxyalkylene adducts oroxyalkylene groups affect the properties of the product, it is desirableto tailor the adduct number distribution of a given product mixture toits intended service. For example, it is known that in surfactantapplications, an adduct with too few ethylene oxide molecules is noteffective because of poor water solubility, while an adduct with toomany ethylene oxide molecules is undesirable because surface tensionreduction per unit mass decreases drastically with increasing molecularweight. Thus, as taught in U.S. Pat. No. 4,239,917, it is desirable,particularly for surfactant applications, to use ethoxylates oralkoxylates with a narrow distribution in the desired mole adduct rangeof from about 5 to about 10 alkylene oxide adducts per alkylatemolecule.

PCT Application WO85/00365 discloses an alkoxylation process whichutilizes a calcium based catalyst to produce alkoxylation productshaving a narrow distribution of alkoxylation species.

U. S. Pat. No. 3,941,606 discloses compositions useful as siccatives inpaints and composed of the reaction product of a polyvalent metalcompound such as an oxide of calcium, a branched chain aliphatic or anon-aromatic cyclic acid, and a polyol or alkoxy alkanol.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a novelprocess for preparing calcium based alkoxylation catalysts havingenhanced activity.

It is further an object of the present invention to produce a calciumbased catalyst for alkoxylation reactions which is stable and showsincreased activity with aging.

Another object of the present invention is to provide a process forpreparing alkoxylation product mixtures having narrow alkoxylationproduct distributions.

The above and other objects of the present invention will becomeapparent from the description given herein and the appended claims.

In one aspect, the present invention provides a process for preparing analkoxylation catalyst in which a catalyst pre-mix is formed by admixingan alkoxylated alcohol, a calcium containing compound which is at leastpartially dispersible in the alkoxylated alcohol, an inorganic acid andan aluminum alkoxide, the calcium compound being added prior to additionof the aluminum alkoxide. The catalyst pre-mix is then heated to atemperature and for a time sufficient to effect at least a partialexchange reaction between the alkoxide groups of the aluminum alkoxideand the hydroxyl group of the alkoxylated alcohol to thereby form anactive alkoxylation catalyst. In another aspect, the present inventionprovides a process for the alkoxylation of an alcohol in which theactive alkoxylation catalyst prepared by the method described above isused in a process wherein an alcohol reactant and an alkylene oxide arebrought together, in the presence of the alkoxylation catalyst and undertypical alkoxylation conditions, to thereby produce alkoxylatedderivatives of the alcohol reactant.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

In preparing the alkoxylation catalyst according to the process of thepresent invention, a catalyst pre-mix is first formed by admixing analkoxylated alcohol, a calcium containing compound which is at leastpartially dispersible in the alkoxylated alcohol, an inorganic acid andan aluminum alkoxide. The alkoxylated alcohols useful in forming thecatalyst are those having the general formula R₁ --O--(CH₂ --CH₂--0)--_(n) H where R₁ is a hydrocarbon radical containing from 1 toabout 30 carbon atoms and n is an average and is from about 2 to about20. Particularly useful are alkoxylated alcohols wherein R₁ is fromabout 8 to about 14, most preferably from about 10 to about 12. Inpreferred alkoxylated alcohols, n is from about 1 to about 12, mostprferably from about 1 to about 4. Thus, ethoxylates of fatty alcoholssuch as decanol and dodecanol wherein there are from about 1 to 12 andmost preferably from 1 to 4 moles of ethylene oxide are especiallypreferred. The R₁ group is generally an organic residue of an aliphaticalcohol which may be of branched or straight chain structure, althoughpreferably, particularly for surfactant use, it is preferred thatgreater than 50%, more preferably greater than 60% and most preferablygreater than 70% of such alcohol molecules are of linear (straightchain) carbon structure.

Specific examples of primary, straight chain monohydric aliphaticalcohols from which the R₁ group can be derived include ethanol,hexanol, octanol, decanol, dodecanol, tetradecanol, pentadecanol,octadecanol, eicosanol, etc. Examples of branched chain or secondaryalcohols from which the R₁ group can be derived include isopropanol,isoheptanol, 3-heptanol, isodecanol, 2-methyl-1-nonanol,2-methyl-1-undecanol, 4-tetradecanol and 4-hexadecanol.

The alkoxylated alcohols used in the catalyst forming process of thepresent invention can be prepared by methods well known in the art forpreparing ethylene oxide adducts of alcohols. Alternately, the ethyleneoxide adducts can be prepared according to the process of the presentinvention.

The calcium containing compound used in the process of the presentinvention is one which is at least partially dispersible in thealkoxylated alcohol. As used herein, the term "dispersible" refers to acalcium compound which solublizes or otherwise interacts with thealkoxylated alcohol in such a manner that it becomes a new species ofcalcium compound. It is to be understood, however, that inasmuch as themechanism is not completely understood, the term "dispersible" or"soluble" is not intended to be limited to the formation of a trulydissolved calcium species as would be commonly understood in the case ofordinary solublization. While compounds such as calcium hydride, calciumacetate, calcium oxalate, calcium nitrate, etc. may be used, it ispreferred that the calcium containing compound be calcium oxide, calciumhydroxide or a mixture thereof.

The inorganic acids useful in the process of the present inventioninclude the acids themselves as well as "acid salts". Thus, non-limitingexamples of inorganic acids include sulphuric acid, hydrochloric acid,hydrofluoric acid, phosphoric acid, pyrophosphoric acid, ammoniumbiflouride, ammonium sulfate, etc. Particularly preferred are the oxyacids, such as sulphuric acid.

The aluminum alkoxide used in the process of the present invention willhave the general formula ##STR1## wherein R₂, R₃ and R₄ is each ahydrocarbon radical containing from about 1 to about 30 carbon atoms.Generally speaking, the description set out above with respect to the R₁radical is generally applicable to the R₂ radical, i.e., the R₂ radicalis generally an organic residue derived from an alcohol. Desirably, thealuminum trialkoxide is obtained by reacting an aluminum trialkyl withethylene followed by oxidation which produces aluminum alkoxides inwhich the chain length of the groups R₂, R₃ and R∝vary. It will beappreciated that while the groups R₂, R₃ and R₄ can each be, andgenerally are, different from one another, they may all be the same. Itis generally preferred to use aluminum alkoxides wherein each of the R₂,R₃ and R₄ groups is such as to provide an average chain length of fromabout 8 to about 14 carbon atoms for all of the R₂, R₃ and R₄.

In preparing the catalyst pre-mix, relative amounts of the variouscomponents can vary widely. For example, the mole ratio of the calciumcompound to the aluminum alkoxide can vary from about 1:1 to about 10:1,based on calcium and aluminum, respectively. The mole ratio of theinorganic acid to the aluminum alkoxide can vary from about 0.25:1 toabout 4:1, based on the ratio of the acid equivalent e.g. acidhydrogens, in the inorganic acid to the aluminum, respectively. It isgenerally preferred that the combined concentration of the calciumcompound, the inorganic acid and the aluminum alkoxide be present in thecatalyst pre-mix in an amount of from about 1 to about 10% by weight,the alkoxylated alcohol and diluents such as free alcohol being presentin an amount of from about 90-99% by weight. Depending on the source andtype of the alkoxylated alcohol, free alcohol content can range fromabout 1% by weight to about 60% by weight.

Generally speaking, the order of addition of the various components ofthe catalyst pre-mix is immaterial with the exception that the calciumcompound must be added prior to addition of the aluminum alkoxide. Thus,although it is common practice in carrying out the process of thepresent invention to admix the alkoxylated alcohol, the calcium compoundand the inorganic acid, followed by the addition of the aluminumalkoxide, the process can also be carried out by reversing the order ofaddition of the aluminum alkoxide and the inorganic acid.

In addition to the above components of the catalyst pre-mix, the pre-mixcan contain, with advantage, organic acids. Suitable organic acids arethose carboxylic acids which have greater miscibility in hydrocarbonsolvents than in water. Such carboxylic acids, which may generally beconsidered fatty acids, have a carbon chain length versus acidfunctionality which provides the greater miscibility or acidfunctionality which provides the greater miscibility or solubility inhydrocarbons. Non-limiting examples of fatty acids include those naturalor synthetic mono-functional carboxylic acids wherein the carbon chainlength is greater than about 5 carbon atoms, generally from about 5 toabout 15 carbon atoms. Specific examples of such suitable acids includehexanoic, octanoic, nonanoic, 2-ethyl hexanoic, neodecanoic,isooctanoic, stearic, napthanoic, and mixtures or isomers of such acids.While it is preferred that the acids, if used, be saturated, they mayoptionally contain other functional groups such as hydroxyl groups,amine groups, etc. which do not interfere with the process. It has beenfound that the use of the fatty acids leads to a better dispersion ofthe calcium compound and that the active catalyst suspension is morestable in terms of the solids remaining dispersed.

In preparing the catalyst according to the process of the presentinvention, a typical alkoxylated alcohol is admixed with a suitablecalcium containing compound such as calcium oxide and the mixturestirred for a suitable period of time until at least some of the calciumcompound disperses or solublizes in the alkoxylated alcohol. Generally,this is accomplished by stirring, or other means of agitation to achieveintimate and thorough contact, at a temperature of generally from about25° C. to about 150° C. (usually below the boiling point of thealkoxylated alcohol) for a sufficient period of time. The dispersiontime can vary from about 0.5 hours to about 20 hours. As can be seen,longer times can be used if desired. Once the dispersion has beenformed, as evidenced, e.g., by the pressure of titratible alkalinity,the inorganic acid is then slowly or incrementally added. The aluminumalkoxide is then added and stirring of the mixture continued and themixture heated to a temperature and for a sufficient period of time toeffect at least a partial exchange reaction between the alkoxide groupsof the aluminum alkoxide and the hydroxyl group of the alkoxylatedalcohol.

The precise temperature to which the catalyst pre-mix is heated will, ofcourse, depend upon the nature of the components employed to form thepre-mix. However, as noted above, the heating of the catalyst pre-mix toactivate it is usually carried out at a temperature and for a period oftime sufficient to effect at least a partial exchange reaction betweenthe alkoxide groups of the aluminum alkoxide and the hydroxyl group ofthe alkoxylated alcohol. This point can generally be determined by theevolution of alcohol which distills out of the mixture. While catalystactivation occurs to some extent with any heating in the desired range,activation is best evidenced by the evolution of alcohol as a result ofthe exchange reaction. However, in order to achieve a highly activecatalyst, it is preferred that the heating be carried on until themixture has reached a substantially constant boiling point. The desiredactivation temperature should, for a given pressure, approximate theboiling point of a substantial fraction of the free alcohols derivedfrom the R₂, R₃ and R₄ group of the aluminum alkoxide. At this point,maximum exchange has likely occurred between the alkoxide groups of thealuminum alkoxide and the hydroxyl group of the alkoxylated alcohol. Itwill be recognized that when the aluminum alkoxide utilized is one whereR₂, R₃ and R₄ are long chain, e.g. 10 to 14 carbon atoms and longer, thealcohols produced in the exchange reaction are high boiling.Accordingly, very little if any distillation of alcohol occurs withoutthe application of extremely high temperatures which can cause unwantedside reactions. In such cases, the heating can be carried out to atemperature of about 190°-300° C. and more preferably from about230°-260° C. Lower temperatures may be employed when the process isconducted under reduced pressure, e.g. at a pressure of about 150-300Torr, temperatures in the range of about 160°C to about 210° C. aresuitable. Indeed, it has been found that reduced pressure results inhighly potent catalysts. For a given catalyst pre-mix, the desiredtemperature range can be determined by sampling the catalyst dispersionas it is being heated at various times during the heating cycle andsubjecting the samples to an ethoxylation reaction. When the desireddegree of activity is achieved in the ethoxylation reaction, heating canbe discontinued and all future catalyst pre-mix of the same compositionheated to that temperature, and, of course, for that period of time.Generally, however, the time of heating can vary from about 0.1 hour toabout 5 hours, generally in the range of from about 0.2 hour to about 1hour.

It has been found that if after the catalyst is prepared it is aged,e.g., by allowing it to stand at room temperature, activity can begreatly enhanced. Although the aging time for a given catalyst pre-mixwill, of course, depend upon the components of that pre-mix, the desiredaging time can be determined in a manner similar to that described abovewith respect to determining the desired temperature and time of heating.Thus, samples of the catalyst which are being aged can be used inethoxylation reactions and the degree of activity determined. Generallyaging times ranging from about two hours to about one week or longer canbe used.

It has been found that in order to make highly active catalysts, it ispreferred that when the catalyst pre-mix is being formed, any waterwhich is present should be removed prior to the addition of the aluminumalkoxide regardless of whether the aluminum alkoxide is added before orafter the addition of the inorganic acid.

To more fully demonstrate the present invention, the followingnon-limiting examples are presented:

EXAMPLE 1

400 grams of an ethoxylated alcohol known as ALFONIC 1412-40¹ marketedby Vista Chemical Company was sparged with nitrogen for one hour. Tothis ethoxylated alcohol was added 30.27 grams of calcium oxide preparedby the calcination of calcium hydroxide at 600° C. for 12 hours. Thismixture was then stirred at 90° C. for 16 hours. To this dispersion wasadded 80.9 grams of an aluminum trialkoxide in which the alkoxide groupshave an average chain length of 10 carbon atoms (mixed 2-30 carbon chainlength) and containing 6% by weight of aluminum. This mixture wasstirred for an additional one hour at 90° C. Concentrated sulphuric acid(18.2 grams) was then added drop wise and the mixture heated to 240° C.as light alcohol and trace water were distilled overhead. The mixturewas cooled and tested for activity.

EXAMPLE 2

The catalyst prepared by Example 1 was tested for activity in makingalcohol ethoxylates. In preparing the ethoxylates, a 60 weight percenttetradecanol/40 weight percent dodecanol mixture was employed as thereactant alcohol. The ethoxylation reaction was conducted at 175° C. and40 psig ethylene oxide pressure. The amount of activated catalystpresent was such as to provide approximately 0.5 grams of metal (calciumplus aluminum) during the reaction. The results are shown below in TableI:

                  TABLE I                                                         ______________________________________                                                                 Percent                                                     Percent  Percent  0-5    Average                                       Reaction                                                                             E.O.     Free     Mole   Moles  Hydroxyl                               Time   Used     Alcohol  Adducts                                                                              E.O.   Number                                 ______________________________________                                        1.74 hr.                                                                             69.72    0.14     1.49   10.74  90.0                                   ______________________________________                                    

EXAMPLE 3

A highly active ethoxylation catalyst was prepared by the addition of37.75 grams of calcium hydroxide to 500 grams of ALFONIC 1412-40 alcoholethoxylate which had been purged with nitrogen for 0.5 hours. Themixture was stirred for 24 hours at 95° C. Sulphuric acid (17.25 grams)was added and 0.5 hour later 128.1 grams of an aluminum alkoxidespecially prepared by exchange of aluminum triisopropoxide with a mixedC₁₂ /C₁₄ alcohol containing approximately 60% by weight C₁₄ alcohol andapproximate 40% by weight C₁₂ alcohol. This mixture was then heated to240° C. bottoms temperature for about 30 minutes. There was very littleoverhead fraction collected. The catalyst Sample 3-1 thus prepared wasused to ethoxylate various alcohols. In addition, the level of catalystrequired was varied in order to test the activity. With this catalyst,it was found that the activity became so high after approximately oneweek of aging at room temperature that the initial stage of theethoxylation was too vigorous at an ethoxylation oxide pressure of 40psig. Accordingly, it was necessary to initiate the ethoxylation at only25 psig, raising the pressure gradually to 40 psig after approximately40 to 50% of the reaction was completed. The results are given below inTable II.

                  TABLE II                                                        ______________________________________                                                                  Per-                                                                          cent       Per-                                            Catalyst Reactant  E.O. Reac- cent Percent                             Catalyst                                                                             Amount   Alcohol   De-  tion  E.O. Free                                Age    Used     Used      sired                                                                              Time  Used Alcohol                             ______________________________________                                        Fresh  10.0 g   60% wt C.sub.14                                                                         70   1.17 hr.                                                                            69.0 0.12                                                40% wt C.sub.12                                               1 Week 5.0 g    60% wt C.sub.14                                                                         70   1.00 hr.                                                                            69.8 0.04                                                40% wt C.sub.12                                               1 Week 2.5 g    60% wt C.sub.14                                                                         70   1.84 hr.                                                                            69.3 0.08                                                40% wt C.sub.12                                               2 Week 10.0 g   60% wt C.sub.8                                                                          60   0.95 hr.                                                                            59.9 1.90                                                40% wt C.sub.10                                               2 Week 5.0 g    60% wt C.sub.14                                                                         60   0.99 hr.                                                                            60.2 0.59                                                40% wt C.sub.12                                               2 Week 5.0 g    60% wt C.sub.10                                                                         60   1.07 hr.                                                                            59.1 1.60                                                40% wt C.sub.12                                               ______________________________________                                    

As a point of reference with respect to Table II, 10.0 grams of thecatalyst provides approximately 0.5 grams of metal (calcium plusaluminum) to the reaction and the total amount of ethoxylate produced is300 grams per batch. Thus, the loading of metal to ethoxylate productrequired is less than 0.17 weight percent. It can be seen that the bestactivity in terms of reaction time was obtained by using aproximately0.09 weight percent metal to ethoxylate ratios.

As can be seen, the catalyst produced in this example shows greateractivity in terms of reaction time than the catalyst produced pursuantto Example 1. Thus, aging of the catalyst affects the activity. Inaddition, it should be noted that using the catalyst produced by theprocess of the present invention, the free alcohol content of theethoxylates is quite low. This is important in the manufacture ofsurfactants since high free alcohol leads to odor problems. Moreover, itis important that spray-dryed ethoxylate not plume. High free alcohol inthe ethoxylates contributes to pluming.

EXAMPLE 4

500 grams of ALFONIC 1412-40 ethoxylated alcohol was purged withnitrogen and heated to 90° C. 37.75 grams of calcium oxide was added andthe mixture stirred for 24 hours. Sulphuric acid (17.25 grams) was addedand the mixture stirred for an hour. A sample of the catalyst (Sample4-1) was taken at this point in the preparation and found to beinactive. Aluminum alkoxide prepared from a mixture of about 60% byweight tetradecanol and about 40% by weight dodecanol was added to aportion of Sample 4-1 catalyst. The addition of the aluminum alkoxidehad no effect as the Sample 4-1 catalyst remained inactive. Theremaining catalyst, without the aluminum compound added, was then heatedto 240° C. for about 30 minutes. A sample of this catalyst (Sample 4-2)was taken and found to be inactive in a standard ethoxylation run. Theaddition of more sulphuric acid to Sample 4-2 up to twice the normalquantity previously used and with further heating to 240° C. alsoresulted in an inactive catalyst (Sample 4-3). This example shows thatthe catalyst, using calcium oxide as the calcium compound, is inactiveprior to the addition of the aluminum alkoxide and heat treatment of themixture.

EXAMPLE 5

To determine if the inactive catalyst Sample 4-2 which did not containaluminum alkoxide could be activated by the addition of aluminumalkoxide and heating, 86.2 grams of Sample 4-2 was added to a reactionvessel and admixed with 20.5 grams of aluminum alkoxide made from amixture of about 60% by weight C₁₄ alcohol and 40% by weight C₁₂alcohol. The temperature was increased to 240° C. (bottoms temperature)and the catalyst tested for activity. The catalyst was now found to beactive for ethoxylation. This catalyst was used in an ethoxylation runusing an alcohol mixture comprised of about 60% by weight tetradecanoland about 40% by weight dodecanol at 175° C. and a 40 psig ethyleneoxide pressure. The reaction time was 4.24 hours. The free alcohol wasfound to be 0.06 weight percent and the hydroxyl number was 96.0.

EXAMPLE 6

To 400 grams of ALFONIC 1412-40 ethoxylated alcohol was added 100 gramsof isopropanol and 32.5 grams of aluminum triisopropoxide. Theisopropanol was distilled overhead to a bottoms temperature of 240° C.Calcium oxide (30.2 grams) was added and the mixture stirred overnightat a temperature of 90° C. Sulphuric acid (13.8 grams) was added andstirring continued at 90° C. for 0.5 hours. The temperature was thenincreased to 240° C. and held for 15 minutes at that temperature. Thecatalyst mixture was cooled and tested for ethoxylation activity andfound to be inactive. This example shows that in the process it isnecessary that the calcium compound be added prior to addition of thealuminum alkoxide to obtain an active catalyst.

EXAMPLE 7

This example demonstrates that the catalyst is much more active if thecalcium compound and the ethoxylated alcohol are stirred or otherwiseagitated for a sufficient period of time in forming the catalystpre-mix. Two preparations were compared, Sample 7-1 and Sample 7-2. Eachpreparation had the same ingredients in common. However, Sample 7-2 wasstirred 16 hours at 90-100° C. while Sample 7-1was stirred 3 hours at150° C. in an attempt to compensate temperature for time. In thepreparations, 300 grams of ALFONIC 1412-70² and 100 grams of ALFONIC1412-40 alcohol ethoxylates were mixed. To this mixture were added 30.2grams of calcium oxide. The stirring times designated were accomplishedprior to adding 80.9 grams of the aluminum alkoxide used in Example 1,stirring 0.5 hours and the addition of 13.6 grams of sulphuric acidfollowed by heating to a bottoms temperature of 240° C. Sample 7-1showed only slight ethoxylation activity whereas sample 7-2 was highlyactive for ethoxylation. Sample 7-2, run under normal ethoxylationconditions, gave 2.21 and 2.2 hour reaction times, free alcohols of 0.15and 0.12 weight percent and hydroxyl numbers of 88.0 and 89.0. Theactual levels of ethylene oxide incorporation for 70 weight percentnormal ethoxylate were 68.62 and 69.63 weight percent with the averagemoles of ethylene oxide per alcohol chain being 10.20 and 10.70,respectively. On the other hand, catalyst preparation 7-1 was virtuallyinactive for alcohol ethoxylation, no ethylene oxide update beingobserved after initiation or after waiting for one hour.

EXAMPLE 8

500 grams of ALPHONIC 1412-40 alcohol ethoxylate containing 5 to 10grams of water was added to a two liter stirred flask. 28.8 grams ofnonanoic acid was added immediately and the mixture heated to 100° C.with stirring. Calcium hydroxide (43.5 grams) was added and the mixturestirred for 16 hours at 100° C. Sulphuric acid (9.0 grams) was added andthe mixture then heated to 170° C. to distill out water. At this point85.0 grams of the aluminum alkoxide used in Example 1 was added and anitrogen purge started. The temperature was increased to 240° C. andheld there for 30 minutes as alcohol distilled out. The reaction productwas then cooled. This catalyst sample was designated Sample 8-1. TableIII shows ethylene oxide adduct distributions for ethoxylated alcoholmade by reacting ethylene oxide with a mixture of about 60% by weighttetradecanol and 40% by weight dodecanol using catalyst Samples 8-1 andSample 3-1.

As can be seen From Table III, using the catalyst with the nonanoicacid, the ethylene oxide adduct distribution shows an average maximumcomponent level below that obtained using catalyst Sample 3-1, i.e.without any nonanoic or other fatty acid. In other words, there is aflattening of the distribution using the catalyst incorporating thefatty acid. However, in certain surfactant applications, such a broaderdistribution can be advantageous.

EXAMPLE 9

A calcium compound dispersion was prepared by adding one kilogram ofALFONIC 1012-40, 16 grams of nonanoic acid, 3 grams water and 87 gramsof calcium hydroxide and heating at 95° C. for 16 hours. The mixture wasthen sparged with nitrogen and heated to 200° C. to remove water. A 330gram aliquot of the calcium pre-mix was mixed with 7.0 grams ofsulphuric acid and 65 grams of the aluminum alkoxide used in Example 1and heated under partial vacuum (220 mm) to 195°C where alcohol began todistill overhead. It was found that 10 grams of the above catalystmixture ethoxylated 90 grams of an alcohol (60% C₁₄ /40% C₁₂) to a 70%ethoxylate at 175° in 51 minutes. It was found that the catalyst was soactive under these conditions that regulation of ethylene oxide into thereactor was initially necessary for temperature control. This exampledemonstrates the desirable effects achieved by conducting the heating ofthe catalyst pre-mix under reduced pressures. Specifically, it can beseen that by using reduced pressure activation, the catalysts run fasterbut produce the same quality of ethoxylates in terms of the content offree alcohols.

                                      TABLE III                                   __________________________________________________________________________    ALCOHOL   PERCENT                                                                             SAMPLE                                                                              PERCENT WITH GIVEN MOLES E.O.                           ETHOXYLATED                                                                             E.O.  NO.   0  1  2  3  4  5  6  7  8  9  10 11                     __________________________________________________________________________    1412CC    69.69 8-1   0.02                                                                             0.01                                                                             0.04                                                                             0.05                                                                             0.14                                                                             0.37                                                                             1.03                                                                             2.64                                                                             5.99                                                                             10.79                                                                            15.43                                                                            17.81                  1412CC    69.06 8-1   0.04                                                                             0.00                                                                             0.03                                                                             0.05                                                                             0.19                                                                             0.52                                                                             1.43                                                                             3.59                                                                             7.65                                                                             12.74                                                                            16.83                                                                            17.86                  1412CC    64.90 3-1   0.14                                                                             0.00                                                                             0.02                                                                             0.02                                                                             0.09                                                                             0.20                                                                             0.55                                                                             1.71                                                                             4.79                                                                             10.36                                                                            16.31                                                                            20.22                  1412CC    70.17 "     0.12                                                                             0.00                                                                             0.01                                                                             0.02                                                                             0.10                                                                             0.23                                                                             0.61                                                                             1.83                                                                             4.90                                                                             10.56                                                                            16.54                                                                            20.02                  1412CC    70.45 "     0.04                                                                             0.00                                                                             0.02                                                                             0.05                                                                             0.09                                                                             0.21                                                                             0.57                                                                             1.74                                                                             4.63                                                                             9.81                                                                             15.50                                                                            19.26                  1412CC    70.57 "     0.08                                                                             0.01                                                                             0.02                                                                             0.07                                                                             0.09                                                                             0.20                                                                             0.54                                                                             1.60                                                                             4.34                                                                             9.39                                                                             15.16                                                                            19.03                  1412CC    70.70 "     0.17                                                                             0.00                                                                             0.01                                                                             0.02                                                                             0.08                                                                             0.17                                                                             0.45                                                                             1.36                                                                             3.89                                                                             8.82                                                                             14.78                                                                            19.22                  1412CC    69.38 "     0.09                                                                             0.00                                                                             0.02                                                                             0.03                                                                             0.14                                                                             0.36                                                                             1.03                                                                             2.85                                                                             6.60                                                                             12.06                                                                            16.79                                                                            18.59                  1412CC    69.38 "     0.09                                                                             0.01                                                                             0.02                                                                             0.03                                                                             0.14                                                                             0.37                                                                             1.05                                                                             2.88                                                                             6.65                                                                             12.08                                                                            16.78                                                                            18.51                  1412CC    69.33 "     0.10                                                                             0.01                                                                             0.03                                                                             0.04                                                                             0.15                                                                             0.38                                                                             1.02                                                                             2.72                                                                             6.26                                                                             11.47                                                                            16.17                                                                            18.22                  1412CC    69.76 "     0.18                                                                             0.00                                                                             0.01                                                                             0.02                                                                             0.09                                                                             0.25                                                                             0.73                                                                             2.22                                                                             5.33                                                                             10.77                                                                            16.84                                                                            18.82                  1412CC    69.90 "     0.09                                                                             0.01                                                                             0.02                                                                             0.03                                                                             0.12                                                                             0.31                                                                             0.82                                                                             2.30                                                                             3.52                                                                             10.54                                                                            13.49                                                                            18.20                  1412CC    69.26 "     0.11                                                                             0.00                                                                             0.01                                                                             0.02                                                                             0.10                                                                             0.35                                                                             1.02                                                                             2.81                                                                             6.70                                                                             12.43                                                                            17.48                                                                            19.22                  1412CC    69.97 "     0.07                                                                             0.01                                                                             0.02                                                                             0.03                                                                             0.15                                                                             0.37                                                                             0.97                                                                             2.50                                                                             3.39                                                                             10.27                                                                            14.74                                                                            17.34                  1412CC    69.19 "     0.08                                                                             0.01                                                                             0.03                                                                             0.06                                                                             0.16                                                                             0.42                                                                             1.20                                                                             3.20                                                                             7.07                                                                             12.27                                                                            16.89                                                                            18.38                  1412CC    68.64 "     0.07                                                                             0.02                                                                             0.05                                                                             0.07                                                                             0.17                                                                             0.50                                                                             1.48                                                                             3.95                                                                             8.48                                                                             14.00                                                                            18.84                                                                            18.21                  1412CC    69.88 "     0.05                                                                             0.01                                                                             0.02                                                                             0.03                                                                             0.04                                                                             0.17                                                                             0.58                                                                             1.91                                                                             5.23                                                                             10.71                                                                            16.54                                                                            19.61                  1412CC    69.33 "     0.11                                                                             0.01                                                                             0.02                                                                             0.03                                                                             0.07                                                                             0.23                                                                             0.79                                                                             2.56                                                                             6.34                                                                             12.45                                                                            17.88                                                                            19.49                  1412CC    69.13 "     0.15                                                                             0.01                                                                             0.03                                                                             0.05                                                                             0.16                                                                             0.44                                                                             1.24                                                                             3.25                                                                             7.15                                                                             12.40                                                                            18.79                                                                            18.10                  AVERAGE   69.72 8-1   0.10                                                                             0.01                                                                             0.02                                                                             0.03                                                                             0.12                                                                             0.30                                                                             0.84                                                                             2.43                                                                             3.80                                                                             11.20                                                                            16.36                                                                            18.83                  AVERAGE   69.30 8-1   0.03                                                                             0.00                                                                             0.03                                                                             0.05                                                                             0.17                                                                             0.44                                                                             1.23                                                                             3.12                                                                             6.82                                                                             11.76                                                                            14.13                                                                            17.83                  __________________________________________________________________________    ALCOHOL   PERCENT                                                                             SAMPLE                                                                              PERCENT WITH GIVEN MOLES E.O.                           ETHOXYLATED                                                                             E.O.  NO.   12 13 14  15 16 17  18 19 20  21 22                     __________________________________________________________________________    1412CC    69.69 8-1   16.49                                                                            12.74                                                                            8.22                                                                              4.55                                                                             2.19                                                                             0.89                                                                              0.32                                                                             0.11                                                                             0.04                                                                              0.01                      1412CC    69.86 8-1   13.39                                                                            10.95                                                                            6.58                                                                              3.41                                                                             1.57                                                                             0.65                                                                              0.22                                                                             0.15                                                                             0.09                                                                              0.05                                                                             0.02                   1412CC    64.90 3-1   10.11                                                                            13.65                                                                            7.95                                                                              3.62                                                                             1.44                                                                             0.47                                                                              0.13                                                                             0.03                             1412CC    70.17 "     18.02                                                                            13.42                                                                            7.83                                                                              3.62                                                                             1.43                                                                             8.49                                                                              0.14                                                                             0.05                             1412CC    70.45 "     13.97                                                                            8.58                                                                             4.33                                                                              1.81                                                                             0.64                                                                             0.18                                                                              0.06                                1412CC    70.57 "     18.52                                                                            14.29                                                                            8.95                                                                              4.65                                                                             1.99                                                                             8.73                                                                              0.25                                                                             0.07                                                                             0.03                          1412CC    70.70 "     18.79                                                                            14.99                                                                            9.43                                                                              4.70                                                                             2.02                                                                             0.76                                                                              0.24                                                                             0.83                             1412CC    69.38 "     16.34                                                                            11.79                                                                            7.04                                                                              3.57                                                                             1.60                                                                             0.65                                                                              0.26                                                                             0.11                                                                             0.03                                                                              0.02                      1412CC    69.38 "     16.29                                                                            11.68                                                                            7.00                                                                              3.60                                                                             1.65                                                                             0.71                                                                              0.31                                                                             0.14                                                                             0.06                                                                              0.03                      1412CC    69.33 "     16.47                                                                            12.23                                                                            7.58                                                                              4.01                                                                             1.88                                                                             0.79                                                                              0.32                                                                             0.13                                                                             0.03                          1412CC    69.76 "     17.42                                                                            12.94                                                                            7.97                                                                              4.11                                                                             1.80                                                                             0.70                                                                              0.25                                                                             0.09                                                                             0.02                          1412CC    69.90 "     17.05                                                                            13.03                                                                            8.31                                                                              4.49                                                                             2.12                                                                             0.91                                                                              0.39                                                                             0.15                                                                             0.06                                                                              0.03                      1412CC    69.26 "     16.50                                                                            11.27                                                                            6.48                                                                              3.17                                                                             1.35                                                                             0.54                                                                              0.22                                                                             0.08                                                                             0.03                          1412CC    69.97 "     16.68                                                                            13.24                                                                            8.82                                                                              4.99                                                                             2.46                                                                             1.09                                                                              0.43                                                                             0.16                                                                             0.06                          1412CC    69.19 "     16.06                                                                            11.42                                                                            6.75                                                                              3.44                                                                             1.53                                                                             0.62                                                                              0.24                                                                             0.10                                                                             0.04                                                                              0.02                                                                             0.01                   1412CC    68.64 "     14.77                                                                            9.87                                                                             5.58                                                                              2.71                                                                             1.18                                                                             0.50                                                                              0.20                                                                             0.09                                                                             0.05                                                                              0.02                                                                             0.01                   1412CC    69.88 "     17.99                                                                            13.07                                                                            7.71                                                                              3.77                                                                             1.59                                                                             0.60                                                                              0.21                                                                             0.07                                                                             0.03                                                                              0.01                      1412CC    69.33 "     16.64                                                                            11.33                                                                            6.53                                                                              3.11                                                                             1.28                                                                             0.48                                                                              0.18                                                                             0.07                                                                             0.02                          1412CC    69.13 "     13.76                                                                            11.28                                                                            6.81                                                                              3.59                                                                             1.62                                                                             0.76                                                                              0.26                                                                             0.10                                                                             0.04                                                                              0.01                      AVERAGE   69.72 8-1   16.79                                                                            12.25                                                                            7.36                                                                              3.70                                                                             1.62                                                                             0.45                                                                              0.24                                                                             0.09                                                                             0.04                                                                              0.02                                                                             0.01                   AVERAGE   69.34 8-1   15.94                                                                            11.85                                                                            7.40                                                                              3.90                                                                             1.88                                                                             0.77                                                                              0.27                                                                             0.13                                                                             0.04                                                                              0.03                                                                             0.018                  __________________________________________________________________________

EXAMPLE 10

Samples of the catalysts made as per the procedure of Example 9 butusing acids other than sulphuric acid were prepared. Thus, catalystswere prepared using hydrochloric acid, formic acid, ammonium bifluoride,carbonated aluminum alkoxide and boron trifluoride. While all of thesecatalysts showed some activity, they were found to be far less activethan the catalyst prepared using sulphuric acid.

EXAMPLE 11

A calcium compound dispersion was prepared by stirring 43.5 grams ofcalcium hydroxide in 500 grams of ALFONIC 1214-0 alcohol ethoxylate for19 hours at 100° C. At this time, 9.2 grams of concentrated sulphuricacid was added slowly, with stirring, and the mixture stirred for anadditional 5 hours. A 100 gram aliquot of this catalyst was removed andheated to 240° C. for thirty minutes to form the activated catalyst. Tengrams of this activated catalyst was used to ethoxylate 90 grams of a60% C_(14/40) % C₁₂ alcohol. The ethoxylation reaction was conducted ata 40 psig ethylene oxide pressure at 175° C. to a 70% by weight ethyleneoxide adduct produced. The ethoxylation data is shown in Table IV below.

                  TABLE IV                                                        ______________________________________                                        Catalyst                                                                              Run      Free      % Polyethylene                                     Age     Time     Alcohol   Glycol    Dioxane                                  ______________________________________                                        Fresh   1.08 hrs 0.25%     0.63%      10 ppm                                  1 month 1.53 hrs 0.02%     0.70%     <10 ppm                                  ______________________________________                                    

EXAMPLE 12

A calcium compound dispersion was made and treated with concentratedsulphuric acid as in the Example above. Following that, 73.7 grams ofaluminum alkoxide made from a 60% C₁₄ /40% C₁₂ alcohol mixture was addedand the entire mixture heated to 240° C. for thirty minutes to form theactive catalyst. It was found that if this catalyst was used under thesame conditions of pressure and temperature as was employed in Example11 for ethoxylation reaction, the reaction could not be controlled.Indeed, the entire reaction was completed in 1.08 hours, including 10-15minutes during which ethylene oxide addition was stopped to allow thetemperature to lower. Because of temperature overruns, no analyticaldata was collected on the ethoxylate produced.

A second ethoxylation run was made with the catalyst prepared by Example12 but this time using 5.0 grams of the catalyst mixture instead of 10grams of catalyst mixture. The ethoxylation temperature was reduced to150° C. to prevent overrun temperatures. While addition of ethyleneoxide was allowed to proceed on demand, the rate of reaction was sorapid that pressure in the reactor did not reach 40 psig until 25minutes into the run. The run was completed in 1.19 hours. Theethoxylation data is shown below in Table V.

                  TABLE V                                                         ______________________________________                                        Free Alcohol                                                                              % Polyethylene Glycol                                                                         Dioxane                                           ______________________________________                                        0.05%       --              30 ppm                                            ______________________________________                                    

Examples 11 and 12 show two important points. Number one, catalystsamples prepared using the aluminum alkoxide show greatly increasedactivity over those which do not contain the aluminum alkoxide.Additionally, it was observed that whereas catalysts which incorporatethe aluminum alkoxide continue to improve with aging (see Example 3,Table II), catalysts prepared without the aluminum alkoxide showeddecreased activity with aging (see Table IV).

The foregoing disclosure and description of the invention isillustrative and explanatory thereof, and various changes in the methodsteps may be made within the scope of the appended claims withoutdeparting from the spirit of the invention.

What is claimed is:
 1. A process for the alkoxylation of an alcoholcomprising:forming a catalyst pre-mix by admixing an alkoxylated alcoholmixture containing an alkoxylated alcohol having the general formula

    R.sub.1 --O--(CH.sub.2 CH.sub.2 --O)--.sub.n H

where R₁ is a hydrocarbon radical containing from about 1 to about 30carbon atoms and n is from about 1 to about 20 and from about 1 to about60% by weight alcohol, a calcium containing compound which is at leastpartially dispersible in said alkoxylated alcohol mixture, an inorganicacid, and an aluminum alkoxide having the general formula ##STR2## whereR₂, R₃ and R₄ is each a hydrocarbon radical containing from about 1 toabout 30 carbon atoms, said calcium containing compound and saidalkoxylated alcohol mixture being mixed prior to addition of saidaluminum alkoxide; heating said catalyst pre-mix to a temperature andfor a time sufficient to effect at least a partial exchange reactionbetween the alkoxide groups of said aluminum alkoxide and said hydroxylgroup of said alkoxylated alcohol and thereby form an activealkoxylation catalyst; and introducing an alcohol reactant and analkylene oxide under alkoxylation conditions to thereby producealkoxylated derivatives of said alcohol reactant.
 2. The process ofclaim 1 wherein R₁ is a hydrocarbon radical containing from about 8 toabout 14 carbon atoms.
 3. The process of claim 1 wherein n is from about1 to about
 12. 4. The process of claim 1 wherein n is from about 1 toabout
 4. 5. The process of claim 1 wherein R₂, R₃ and R₄ is each ahydrocarbon radical containing from about 8 to about 14 carbon atoms. 6.The process of claim 1 wherein said calcium containing compound isselected from the group consisting of calcium oxide, calcium hydroxideand mixtures thereof.
 7. The process of claim 1 wherein said inorganicacid is selected from the group consisting of sulphuric acid andhydrochloric acid.
 8. The process of claim 1 wherein the mole ratio ofsaid calcium containing compound to said aluminum alkoxide is from about1:1 to about 10:1, calculated as calcium and aluminum, respectively. 9.The process of claim 1 wherein the mole ratio of said inorganic acid tosaid aluminum alkoxide is from about 0.25:1 to about 4:1, calculated asacidic hydrogen and aluminum, respectively.
 10. The process of claim 1including adding to said pre-mix an organic acid which is more readilymiscible in hydrocarbon solvents than in water.
 11. The process of claim1 including removing water from said pre-mix prior to the addition ofsaid aluminum alkoxide.
 12. The process of claim 1 wherein said alkyleneoxide comprises ethylene oxide.
 13. The process of claim 1 wherein saidalcohol reactant is a monohydric aliphatic alcohol containing from 8 to14 carbon atoms.